CN105542148B - A kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell and its preparation method and application - Google Patents
A kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell and its preparation method and application Download PDFInfo
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- CN105542148B CN105542148B CN201510976625.6A CN201510976625A CN105542148B CN 105542148 B CN105542148 B CN 105542148B CN 201510976625 A CN201510976625 A CN 201510976625A CN 105542148 B CN105542148 B CN 105542148B
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- exchange membrane
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- fuel cell
- polymer electrolyte
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 53
- 239000000446 fuel Substances 0.000 title claims abstract description 38
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 27
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 13
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000005349 anion exchange Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 11
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 80
- 239000000178 monomer Substances 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 20
- 125000005843 halogen group Chemical group 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000005893 bromination reaction Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 230000002596 correlated effect Effects 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000008676 import Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002952 polymeric resin Substances 0.000 description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 150000008614 2-methylimidazoles Chemical class 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- -1 Arylene ether compound Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920000090 poly(aryl ether) Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940009844 combination benzoyl peroxide Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
Abstract
The present invention discloses a kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell and its preparation method and application.The novel anionic exchange membrane, has the structure as shown in formula (I).Novel anionic exchange membrane provided by the present invention available for alkaline fuel cell is prepared by the polyether sulfone containing quaternary ammonium salt ion-exchange group or polyether ketone polymer, polyether sulfone or the polyether ketone polymer main chain has relatively good mechanical performance and heat endurance, quaternary ammonium salt ion-exchange group mass contg is controllable and has relatively good chemical stability and ion-exchange performance, the anion-exchange membrane of preparation has higher ionic conductance, good heat endurance and alkaline stability, it disclosure satisfy that the requirement of alkaline polymer electrolyte fuel cell anion-exchange membrane, there is relatively good application prospect in terms of alkaline fuel cell.
Description
Technical field
The invention belongs to ion exchange membrane material field, and in particular to a kind of poly- containing cyclohexane group and quaternary ammonium salt side
Arylene ether compound, its anion-exchange membrane and its preparation method and application.
Background technology
In the past few decades, polymer electrolyte fuel cells (PEFCs) because efficiently, cleaning the features such as be considered as most
One of generating equipment of with prospects.Proton Exchange Membrane Fuel Cells (PEMFCs), due to there are fuel infiltration, need to use it is expensive
The defects of metallic catalyst and intermediate product can cause poison electrode catalysts, hindering it, further development and the marketization should
With.
Alkaline polymer electrolyte fuel cell (AEMFCs), as a kind of fuel cell skill to work under alkaline environment
Art, compared with Proton Exchange Membrane Fuel Cells, has following obvious advantage：
(1) fuel and oxidant at negative and positive the two poles of the earth can be effectively obstructed, methanol permeability is low；(2) have than in proton
Faster reaction speed in exchange film fuel battery；(3) poison electrode catalysts will not be caused；(4) avoid having to using expensive
The situation of metallic catalyst, can select the non-precious metal catalysts such as silver, cobalt, nickel, greatly reduce production cost.
As the important component of alkaline polymer electrolyte fuel cell, the performance of anion-exchange membrane fires alkalescence
The performance of material battery has material impact.Anion-exchange membrane in alkaline polymer electrolyte fuel cell it is necessary to have than
Higher ionic conductivity, high chemical stability and heat endurance and good mechanical performance etc..Anion-exchange membrane
Main chain is generally made of polyarylether class compound or fatty-chain polymers, and side base is made of electrically charged quaternary ammonium salt group.Poly- virtue
Ether compound has remarkable heat endurance, mechanical performance and corrosion resistance, and field of membrane material is exchanged in fuel cell ion
It is widely applied.Ionic conductivity and chemical stability are the bottlenecks of current anion exchange membrane technology development.
M.Tanaka etc. (Journal of the American Chemical Society, 2011,133,10646-10654) reports
The quaternary ammonium salt polyether compound of close and distant aqueous phase separation is prepared using the fluorenyl this group containing big steric hindrance come improve it is cloudy from
The ionic conductivity and chemical stability of proton exchange.Qing Lin Liu et al. (ACS Applied Materials＆
Interfaces, 2015,7,8284-8292) by introducing this big steric hindrance of phenolphthalein and nonplanar virtue on main polymer chain
The ionic conductivity of anion-exchange membrane prepared by perfume base group reaches 146mS/cm at 80 DEG C, and in 2M KOH, 60 DEG C
Remain to make ionic conductivity be maintained at 70mS/cm or so after placing 25 days.Document (K.Miyatake, Polymer
Chemistry, 2011,2,1919-1929) to report, the molecular radical of fluorenes, phenolphthalein and this big steric hindrance of hexamethylene is conducive to improve
Free volume in the heat endurance and chemical stability and film of anion-exchange membrane, is conducive to improve ionic conductance.This
Patent description by hexamethylene it is this equally there is larger steric hindrance and nonplanar group to introduce polyarylether polymer main chain favourable
In the ionic conductance, chemical stability and the thermal stability that improve its anion-exchange membrane, anion exchange can be used as
Film is applied in alkaline polymer fuel cell.
The content of the invention
It is an object of the invention to be in view of the deficiencies of the prior art, there is provided one kind can be used for alkaline polymer to be electrolysed
The polyether sulfone anion-exchange membrane of matter fuel cell, the anion-exchange membrane have higher ionic conductivity, chemical stabilization
Property, heat endurance and mechanical performance.Anion-exchange membrane main chain of the present invention is polyether sulfone or polyether ketone polymer, is had good
Mechanical performance and thermal stability, side base be containing in trimethylamine, N- methylimidazoles, 1,2- methylimidazoles, pyridine, guanidine
Any one, has good ion exchanging function and chemical stability.
Technical scheme is as follows：
A kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell, is as shown in formula (I)
The polyether compound containing cyclohexane group and quaternary ammonium salt side：
Wherein m and n represents the degree of polymerization, m=1~200 and n=0~200, and 0<M/ (m+n)≤1, the average molecular of polymer
Measure as 10000~100000；R1、R2Each stand alone as hydrogen atom, methyl or quaternary ammonium salt group.
Preferably,The one kind being each independently selected from formula (1)~formula (3)：
Work as R1=R2During=H, preferablyAny one in formula (4)~formula (6)：
Work as R1=Q, R2=H or R1=H, R2=Q or R1=R2During=Q, preferablySelected from formula (7)~formula (9)
In any one：
Wherein Q can be any one in following several substituents：
Wherein, X is the anion with negative one valence charge, can be Br-, Cl-Or OH-。
According to the present invention, the formula (I) is random copolymer.
By controlling the ratio that feeds intake, the ratio of m and n components can be controlled, the numerical value of m and n reflect polyarylether chemical combination
The molecular weight and range of molecular weight distributions of thing.
Another object of the present invention is to provide the above-mentioned polyether compound containing cyclohexane group and quaternary ammonium salt side
Preparation method.
The method of the present invention comprises the following steps：
Step (1), by bisphenol cyclohexane monomer, biphenol monomer B, the fragrant monomer A containing halogen atom, it is former to contain halogen
The fragrant monomer C and catalyst of son are according to molar ratio 1：(0~199):1：(0~199)：(2.5~500) are added to reaction and hold
Device, then adds water entrainer and polar non-solute p, after reacting 3h at 140 DEG C, be warming up to 150~210 DEG C of reactions 3~
16h, reactant is poured into ethanol and is separated out, and is washed repeatedly 3 times with ethanol and deionized water, is dried in vacuo 24h at 80 DEG C, is obtained
To polyether compound CHPES；The volume ratio of the water entrainer and polar non-solute p is (0.2~0.4):1；
The biphenol monomer B need to be added at the same time with the fragrant monomer C containing halogen atom, or not added at the same time.
1. work as R1=R2During=H：
The biphenol monomer containing hexamethylene has such as lower structure：
The B containing biphenol monomer has such as lower structure：WhereinChoosing
From any one in formula (11)~formula (13):
The fragrant monomer A and C containing halogen atom have such as lower structure：
WhereinIt is each independently selected from any one in formula (14)~(16)
Kind:
2. work as R1=Q, R2=H or R1=H, R2=Q or R1=R2During=Q：
The cyclohexane monomer has such as any one in following formula (17)~formula (19) structure：
The biphenol monomer B has such as lower structure：WhereinChoosing
From any one in formula (20)~formula (22)：
The fragrant monomer containing halogen atomWith same above formula
(14)~formula (16) structure.
Step (2), the enpara class that the middle polyether compound CHPES prepared of step (1) is dissolved in certain volume are molten
In agent, suitable bromating agent and initiator are then added, carries out 5~8h of bromination reaction at a certain temperature, pours into ethanol and sinks
Form sediment, then washed repeatedly with ethanol 3 times, 60 DEG C of vacuum drying obtain brominated product BCHPES；The polyether compound
CHPES, alkyl halide varsol, the mass ratio of bromating agent and initiator are 1：(24.70~31.90)：(1.27~2.0304)：
(0.0583~0.086).
Step (3), by after brominated product BCHPES is dissolved in polar non-solute q described in step (2), add quaternized
Reagent, reaction overnight 24h at 50 DEG C, obtains quaternized products QCHPES；The brominated product BCHPES, aprotic, polar are molten
The mass ratio of agent q and quaternizing agent is 1：9：(0.32~10).
Step (4), by obtained quaternized products QCHPES coated in prior level-off clean glass plate above, 50 DEG C
Lower dry 24h is so that solvent volatilization completely, film is taken off above glass plate, obtains the anion-exchange membrane, by prepared by
Anion-exchange membrane be assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery and test correlated performance.
Preferably, the polar non-solute p described in step (1), the polar non-solute q in step (3) be each
Stand alone as n,N-dimethylacetamide, n,N-Dimethylformamide, sulfolane, 1-methyl-2-pyrrolidinone, in dimethyl sulfoxide (DMSO)
It is a kind of.
Preferably, the water entrainer described in step (1) is toluene.
Preferably, the catalyst described in step (1) is potassium carbonate, any one in sodium carbonate or cesium carbonate.
Preferably, the polymeric reaction temperature described in step (1) is 150~210 DEG C.
Preferably, enpara class solvent described in step (2) is 1,1,2,2- tetrachloroethanes, 1,2- dichloroethanes, tetrachloro
Change any one in carbon.
Preferably, initiator described in step (2) is any one in benzoyl peroxide or azodiisobutyronitrile.
Preferably, bromating agent described in step (2) is any one in N- bromo-succinimides or C5H6Br2N2O2.
Preferably, the bromination reaction temperature described in step (2) is 75~85 DEG C.
Preferably, quaternizing agent described in step (3) is trimethylamine, N- methylimidazoles, 1,2- methylimidazole, pyridine
With any one in guanidine.
A further object of the present invention is to provide above-mentioned containing the friendship of the polyarylether anion of cyclohexane group and quaternary ammonium salt side
Film is changed, can be applied in alkaline polymer electrolyte fuel cell and all-vanadium flow battery.
Preparation method and application described in the method for the present invention for optimization scheme, reaction monomers of the present invention, temperature,
Time and other correlated response conditions are the claimed content of this patent, and this patent is claimed to be not limited only to
This.
Compared with prior art, the present invention has the advantages that：
(1) present invention prepares a series of the poly- of excellent performances from Molecular Design and polymer performance angle
Arylene ether compound and its anion-exchange membrane, raw material are easy to get, and preparation process is simple, and cost is low.
(2) polyether compound main chain of the present invention contains the nonplanar cyclohexane group of big steric hindrance, while contains in molecule
More fragrant phenyl ring and ehter bond, had not only improved the intensity of polymer but also had added the flexibility of molecule.
(3) present invention it also avoid the use of cancer causing agents chloromethyl ether in conventional ion exchange membrane preparation process at the same time.
(4) anion-exchange membrane prepared by the present invention has higher ionic conductivity, good heat endurance, machinery
Performance and chemical stability, while have than relatively low electrolyte permeability performance, alkali can be applied to as proton exchange membrane
In property polymer electrolyte fuel cells and all-vanadium flow battery, the self-discharge performance of battery can be effectively reduced.
Brief description of the drawings
Fig. 1 is the resin of polyether compound containing hexamethylene CHPES, brominated hexamethylene polyether compound BCHPES and season
The nuclear-magnetism figure of ammonium anion-exchange membrane QCHPES；
Fig. 2 is for hexamethylene polyether compound resin, bromination cyclohexane product and containing the red of quaternized anion-exchange membrane
External spectrum；
Fig. 3 is the electrical conductivity of the hydroxyl form anion-exchange membrane containing cyclohexane group and quaternary ammonium salt side；
Fig. 4 is the heat endurance curve of the anion-exchange membrane containing hexamethylene and quaternary ammonium salt side.
Embodiment
It is for further analysis to the present invention with reference to specific embodiment.
Embodiment 1
By the cyclohexane monomer (formula 10) of 10mmol, the biphenol monomer B (formula 11) of 10mmol, the halogen atom-containing of 10mmol
Fragrant monomer A (formula 14) and the fragrant monomer C (formula 14) of halogen atom-containing of 10mmol be added to equipped with water knockout drum, blender
In the three-necked flask of the 250ml of import and export of nitrogen, the potassium carbonate of 50mmol is added as catalyst, the toluene of 30ml is as band
Aqua, adds the sulfolane of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C of reaction 3h, polymer solution is fallen
Enter in ethanol and precipitate, and washed repeatedly 3 times with ethanol and deionized water, be dried in vacuo 24h at 80 DEG C, obtain white polymer tree
Fat CHPES, yield 92%；The hexamethylene resin (CHPES) of 1g is dissolved in the 1,1,2,2- tetrachloroethanes of 20ml (31.86g)
In, the N- bromo-succinimides of 1.27g are added as the benzoyl peroxide of bromating agent and 0.086g as initiator, nitrogen
Lower 85 DEG C of progress bromination reaction 5h is protected, pours into ethanol solution and precipitates after being cooled to room temperature, wash 3 times repeatedly with ethanol, 60
Vacuum drying obtains white fibrous product BCHPES at DEG C；0.5g BCHPES are taken to be dissolved in the DMAC N,N' dimethyl acetamide of 4.5g
10% solution is formed in the three-necked flask of 50ml, afterwards 1, the 2- methylimidazoles of addition 0.2g, reaction overnight 24h at 50 DEG C,
On clean glass plate coated in prior leveling, dried at 50 DEG C, obtain the anion-exchange membrane.By prepared anion
Exchange membrane is assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow battery respectively, tests correlated performance.
The resin of polyether compound containing hexamethylene CHPES, brominated hexamethylene polyether compound BCHPES and quaternized
The proton nuclear magnetic spectrogram of anion-exchange membrane QCHPES is as shown in Figure 1, in the proton nuclear magnetic spectrogram of CHPES resins, at 2.0ppm
There is a strong signal peak, this is the benzyl methyl signals in formula (1)；Signal peak at 1.5ppm and 2.3ppm is believed for methylene
Number, it is the signal peak in phenyl ring with sulfuryl adjacent protons at 8.0ppm, shows the formation of sulfuryl polymer.Brominated product BCHPES
Nuclear-magnetism in, be bromomethyl peak at 4.2ppm, show that brominated product is formed.In the nuclear-magnetism figure of anion-exchange membrane QCHPES
The appearance of 3.5ppm and 2.5ppm signal peaks shows that 1,2- methylimidazoles are successfully incorporated into above polymer pendant groups, 5.3ppm
Locate the benzyl methyl signals peak to be connected with DMIZ 1,2 dimethylimidazole.
Fig. 2 hands over for hexamethylene polyether compound resin CHPES, bromination cyclohexane product BCHPES and quaternized anion
Change the infrared spectrogram of film QCHPES.1658cm in figure-1Absworption peak is C-N keys on imidazole ring.1600cm-1And 1488cm-1Respectively
For the absworption peak of C=C and C=N on phenyl ring and imidazoles.
The ionic conductivity of quaternized anion-exchange membrane manufactured in the present embodiment is as shown in QCHPES-1 in Fig. 3,30 DEG C
When film ionic conductivity in deionized water be 6.2mS/cm, 80 DEG C of whens, reach 15.5mS/cm.
Embodiment 2
By the hexamethylene (formula 10) of 10mmol, the biphenol monomer B (formula 12) of 10mmol, the virtue of the halogen atom-containing of 10mmol
The fragrant monomer C (formula 15) of the halogen atom-containing of fragrant monomer A (formula 15) and 10mmol is added to equipped with water knockout drum, blender and nitrogen
In the 250ml three-necked flasks of gas inlet and outlet, the toluene of 30ml adds the sodium carbonate of 50mmol as catalyst as water entrainer,
Add 100ml n,N-dimethylacetamide be used as solvent, 140 DEG C reaction 3h, after be warming up to 165 DEG C react 12h, by polymer
Solution is poured into ethanol solution and precipitated, and washing vacuum drying 24h at 3 times, 80 DEG C repeatedly with ethanol and deionized water obtains white
Fluoropolymer resin CHPES, yield 90%；The hexamethylene resin (CHPES) of 1g is dissolved in the 1,1,2,2- tetra- of 20ml (31.86g)
In chloroethanes, the N- bromo-succinimides for adding 1.27g are used as initiation as the benzoyl peroxide of bromating agent and 0.086g
Agent, the lower 85 DEG C of progress bromination reaction 5h of nitrogen protection, pours into ethanol solution after cooling and precipitates, 3 are washed repeatedly with ethanol
Secondary, 60 DEG C of vacuum drying obtain white fibrous product BCHPES；0.5g BCHPES are taken to be dissolved in the 1-methyl-2-pyrrolidinone of 4.5g
10% solution is formed in the three-necked flask of 50ml, afterwards the N- methylimidazoles of addition 0.18mg, reaction overnight 24h at 50 DEG C, applies
Apply on the clean glass plate of prior leveling, dried at 50 DEG C, obtain the anion-exchange membrane, prepared anion is handed over
Change film to be assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
The ionic conductivity of quaternized anion-exchange membrane manufactured in the present embodiment is as shown in QCHPES-2 in Fig. 3,30 DEG C
When film ionic conductivity in deionized water be 10.5mS/cm, 80 DEG C of whens, reach 26.5mS/cm.
Embodiment 3
By the cyclohexane monomer (formula 10) of 2mmol, the biphenol monomer B (formula 13) of 18mmol and the halogen atom-containing of 2mmol
Fragrant monomer A (formula 15) and the fragrant monomer C (formula 15) of halogen atom-containing of 18mmol be added to equipped with water knockout drum, thermometer
In the three-necked flask of the 250ml of import and export of nitrogen, the toluene of 20ml as water entrainer, urge by the cesium carbonate conduct for adding 50mmol
Agent, adds the n,N-Dimethylformamide of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 150 DEG C of reaction 16h, will
Polymer solution is poured into ethanol solution and precipitated, and is washed 3 times with deionized water and ethanol solution, is dried in vacuo at 80 DEG C repeatedly
24h obtains white polymer resin CHPES, yield 94%；The hexamethylene resin (CHPES) of 1g is dissolved in 20ml's (24.70g)
In 1,2- dichloroethanes, the N- bromo-succinimides for adding 1.27g are made as the benzoyl peroxide of bromating agent and 0.086g
For initiator, the lower 80 DEG C of progress bromination reaction 6h of nitrogen protection, cools to pour into ethanol solution and precipitates, and with ethanol repeatedly
Washing 3 times, 60 DEG C of vacuum drying obtain white fibrous product BCHPES；Take 0.5g BCHPES be dissolved in the sulfolane of 4.5g in
10% solution is formed in the three-necked flask of 50ml, reaction overnight 24h at rear 50 DEG C of 1,2- methylimidazoles for adding 0.2g, coating
On the clean glass plate of prior leveling, dried at 50 DEG C, obtain the anion-exchange membrane.By prepared anion exchange
Film is assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow battery respectively, tests correlated performance.
QCHPES-3 is the ionic conductivity curve of quaternized anion-exchange membrane manufactured in the present embodiment in Fig. 3, from figure
In as can be seen that the ionic conductivity of the film in deionized water is 11.2mS/cm at 30 DEG C, 80 DEG C of whens, reach 37.6mS/cm.
Embodiment 4
By the cyclohexane monomer (formula 17) of 10mmol, the biphenol monomer B (formula 20) of 10mmol, the halogen atom-containing of 10mmol
Fragrant monomer A (formula 14) and the fragrant monomer C (formula 14) of halogen atom-containing of 10mmol be added to equipped with water knockout drum, thermometer
In the three-necked flask of the 250ml of import and export of nitrogen, the toluene of 30ml as water entrainer, urge by the potassium carbonate conduct for adding 50mmol
Agent, adds the sulfolane of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C of reaction 3h, being cooled to room temperature will be poly-
Polymer solution is poured into ethanol solution and precipitated, and is washed repeatedly 3 times with deionized water and ethanol solution, 24h is dried in vacuo at 80 DEG C
Obtain white polymer resin CHPES, yield 93%；The hexamethylene resin (CHPES) of 1g is dissolved in the tetrachloro of 20ml (31.9g)
Change in carbon, the N- bromo-succinimides for adding 1.27g are used as initiation as the azodiisobutyronitrile of bromating agent and 0.0583g
Agent, the lower 75 DEG C of progress bromination reaction 8h of nitrogen protection, cools to pour into ethanol and precipitates, and washs 3 times repeatedly with ethanol, and 60
DEG C vacuum drying obtains white fibrous product BCHPES；The brominated product BCHPES of 0.5g is taken to be dissolved in the N of 4.5g, N- dimethyl
Formamide forms 10% solution in the three-necked flask of 50ml, and it is anti-overnight that the rear pyridine for adding 0.17g reacts 24h at 50 DEG C
Should, on the clean glass plate coated in prior leveling, dried at 50 DEG C, obtain the anion-exchange membrane, by prepared the moon
Amberplex is assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow battery respectively, tests correlated performance.
QCHPES-4 is the ionic conductivity curve of quaternized anion-exchange membrane manufactured in the present embodiment in Fig. 3, from figure
In as can be seen that increased trend is presented with the rise of temperature in the electrical conductivity of the anion-exchange membrane in deionized water, 30
DEG C when film ionic conductivity in deionized water be 33.8mS/cm, 80 DEG C of whens, reach 42.2mS/cm.
The heat endurance of the anion-exchange membrane QCHPES-4 prepared in the embodiment is as shown in figure 4, can from figure
Go out, the fracture of anion-exchange membrane QCHPES-4 side bases occurs at 261 DEG C, and main chain break occurs at 382 DEG C.
Embodiment 5
By the cyclohexane monomer (formula 18) of 15mmol, the biphenol monomer B (formula 21) of 5mmol, the halogen atom-containing of 15mmol
Fragrant monomer A (formula 15) and the fragrant monomer C (formula 15) of halogen atom-containing of 5mmol be added to equipped with water knockout drum, thermometer
In the three-necked flask of the 250ml of import and export of nitrogen, the toluene of 40ml as water entrainer, urge by the sodium carbonate conduct for adding 50mmol
Agent, adds the 1-methyl-2-pyrrolidinone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 200 DEG C of reaction 5h, will polymerize
Thing solution, which is poured into ethanol solution, to be precipitated, and washing vacuum drying 24h at 3 times, 80 DEG C repeatedly with deionized water and ethanol solution obtains
To white polymer resin CHPES, yield 95%；The hexamethylene resin (CHPES) of 1g is dissolved in the 1,1 of 20ml (31.86g),
In 2,2- tetrachloroethanes, the N- bromo-succinimides for adding 1.27g are made as the benzoyl peroxide of bromating agent and 0.086g
For initiator, the lower 85 DEG C of progress bromination reaction 5h of nitrogen protection, cools to pour into ethanol and precipitates, and washed repeatedly with ethanol
3 times, 60 DEG C of vacuum drying obtain white fibrous product BCHPES；The BCHPES of 0.5g is taken to be dissolved in the N of 4.5g, N- dimethyl second
Acid amides forms 10% solution in the three-necked flask of 50ml, on the clean glass plate coated in prior leveling, is dried at 50 DEG C, will
Film is taken off from glass plate and is steeped in the trimethylamine solution that 5g mass fractions are 30%, 50 DEG C of reaction 24h, obtain it is described it is cloudy from
Proton exchange.Prepared anion-exchange membrane is assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow electricity respectively
Chi Zhong, tests correlated performance.
QCHPES-4 is the ionic conductivity curve of quaternized anion-exchange membrane manufactured in the present embodiment in Fig. 3, from figure
In as can be seen that increased trend is presented with the rise of temperature in the electrical conductivity of the anion-exchange membrane in deionized water, 30
DEG C when film ionic conductivity in deionized water be 34.5mS/cm, 80 DEG C of whens, reach 73.3mS/cm.
The heat endurance of the anion-exchange membrane QCHPES-5 prepared in the embodiment is as shown in figure 4, can from figure
Go out, the fracture of anion-exchange membrane QCHPES-5 side bases occurs at 262 DEG C, and main chain break occurs at 380 DEG C.
Embodiment 6
By the cyclohexane monomer (formula 19) of 10mmol, the biphenol monomer B (formula 22) of 10mmol, the halogen atom-containing of 10mmol
Fragrant monomer A (formula 16) and the fragrant monomer C (formula 16) of halogen atom-containing of 10mmol be added to equipped with water knockout drum, thermometer
In the three-necked flask of the 250ml of import and export of nitrogen, the toluene of 30ml as water entrainer, urge by the sodium carbonate conduct for adding 50mmol
Agent, adds the sulfolane of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C of reaction 3h, polymer solution is fallen
Enter in ethanol solution and precipitate, washing at 3 times, 80 DEG C dry 24h in vacuum drying oven repeatedly with deionized water and ethanol solution obtains
White polymer resin CHPES, yield 95%；The hexamethylene resin (CHPES) of 1g is dissolved in 1, the 2- bis- of 20ml (24.70g)
In chloroethanes, the C5H6Br2N2O2 of 2.0304g is added as the benzoyl peroxide of bromating agent and 0.086g as initiator, nitrogen
Lower 80 DEG C of progress bromination reaction 6h is protected, cools to pour into ethanol and precipitates, and washed repeatedly with ethanol 3 times, 60 DEG C of vacuum
It is dried to obtain white fibrous product BCHPES；The brominated product BCHPES of 0.5g is taken to be dissolved in the n,N-Dimethylformamide of 4.5g
10% solution is formed in the three-necked flask of 50ml, 24h reaction overnights is reacted at rear 50 DEG C of guanidine for adding 0.16g, is adjusted in advance
Coat on flat clean glass plate, dried at 50 DEG C, obtain the anion-exchange membrane.By prepared anion-exchange membrane point
It is not assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow battery, tests correlated performance.
Embodiment 7
By the cyclohexane monomer (formula 10) of 5mmol, the biphenol monomer B (formula 11) of 15mmol and the halogen atom-containing of 5mmol
Fragrant monomer A (formula 14) and 15mmol halogen atom-containing fragrant monomer C (15) be added to equipped with water knockout drum, thermometer and
In the three-necked flask of the 250ml of import and export of nitrogen, the toluene of 40ml adds the cesium carbonate of 50mmol as catalysis as water entrainer
Agent, adds the dimethyl sulfoxide (DMSO) of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 180 DEG C of reaction 10h, polymer is molten
Liquid is poured into ethanol and precipitated, and washing at 3 times, 80 DEG C dry 24h in vacuum drying oven repeatedly with deionized water and ethanol solution obtains
White polymer resin CHPES, yield 94%；The hexamethylene resin (CHPES) of 1g is dissolved in the 1,1,2 of 20ml (31.86g),
In 2- tetrachloroethanes, azodiisobutyronitrile conduct of the N- bromo-succinimides of 1.27g as bromating agent and 0.0583g is added
Initiator, the lower 85 DEG C of progress bromination reaction 5h of nitrogen protection, cools to pour into ethanol and precipitates, and wash 3 repeatedly with ethanol
Secondary, 60 DEG C of vacuum drying obtain white fibrous product BCHPES；Take 0.5g BCHPES be dissolved in the dimethyl sulfoxide (DMSO) of 4.5g in
10% solution is formed in the three-necked flask of 50ml, reaction overnight 24h at rear 50 DEG C of 1,2- methylimidazoles for adding 0.2g, in thing
Coat on the clean glass plate of first leveling, dried at 50 DEG C, obtain the anion-exchange membrane.By prepared anion exchange
Film is assembled into alkaline polymer electrolyte fuel cell and all-vanadium flow battery respectively, tests correlated performance.
Embodiment 8
By the cyclohexane monomer (formula 10) of 0.1mmol, the biphenol monomer B's (formula 11) and 0.1mmol of 19.9mmol is halogen
The fragrant monomer C (formula 15) of the halogen atom-containing of the fragrant monomer A (formula 14) and 19.9mmol of plain atom, which is added to be equipped with, divides water
In the three-necked flask of the 250ml of device, thermometer and import and export of nitrogen, the toluene of 30ml adds the carbon of 50mmol as water entrainer
Sour sodium adds the sulfolane of 100ml as solvent as catalyst, 140 DEG C of reaction 3h, after be warming up to 210 DEG C of reaction 3h, will
Polymer solution is poured into ethanol solution and precipitated, and is washed repeatedly at 3 times, 80 DEG C in vacuum drying oven with deionized water and ethanol solution
Dry 24h obtains white polymer resin CHPES, yield 94%；The hexamethylene resin (CHPES) of 1g is dissolved in 20ml
The 1 of (31.86g), in 1,2,2- tetrachloroethanes, adds the N- bromo-succinimides of 1.27g as bromating agent and 0.086g
Benzoyl peroxide as initiator, the lower 85 DEG C of progress bromination reaction 5h of nitrogen protection, cools to pour into ethanol and precipitates,
And washed repeatedly with ethanol 3 times, 60 DEG C of vacuum drying obtain white fibrous product BCHPES；Take the brominated product of 0.5g
The n,N-dimethylacetamide that BCHPES is dissolved in 4.5g forms 10% solution in the three-necked flask of 50ml, rear to add the 1 of 0.2g,
Reaction overnight 24h at 50 DEG C of 2- methylimidazoles, on the clean glass plate coated in prior leveling, dries at 50 DEG C, obtains institute
State anion-exchange membrane.Prepared anion-exchange membrane is assembled into alkaline polymer electrolyte fuel cell and full vanadium respectively
In flow battery, correlated performance is tested.
Embodiment 9
The fragrant monomer A (formula 14) of the cyclohexane monomer (formula 10) of 20mmol and the halogen atom-containing of 20mmol is added to
In the three-necked flask of 250ml equipped with water knockout drum, thermometer and import and export of nitrogen, the toluene of 30ml is added as water entrainer
The potassium carbonate of 50mmol adds the sulfolane of 100ml as solvent as catalyst, 140 DEG C of reaction 3h, after be warming up to 210 DEG C
4h is reacted, polymer solution is poured into ethanol and is precipitated, vacuum at 3 times, 80 DEG C is washed repeatedly with deionized water and ethanol solution
Dry 24h obtains white polymer resin CHPES, yield 94% in baking oven；The hexamethylene resin (CHPES) of 1g is dissolved in 20ml
The 1 of (31.86g), in 1,2,2- tetrachloroethanes, adds the N- bromo-succinimides of 1.27g as bromating agent and 0.086g
As initiator, the lower 85 DEG C of progress bromination reaction 5h of nitrogen protection, pours into ethanol and precipitates, be used in combination benzoyl peroxide after cooling
Ethanol washs 3 times repeatedly, and 60 DEG C of vacuum drying obtain white fibrous product BCHPES；Take the brominated product BCHPES of 0.5g molten
10% solution is formed in the three-necked flask of 50ml in the 1-methyl-2-pyrrolidinone of 4.5g, rear 1, the 2- dimethyl miaows for adding 0.2g
Reaction overnight 24h at 50 DEG C of azoles, on the clean glass plate coated in prior leveling, dries at 50 DEG C and is taken off from glass plate
Under, obtain the anion-exchange membrane.Prepared anion-exchange membrane is assembled into alkaline polymer electrolyte fuel respectively
In battery and all-vanadium flow battery, correlated performance is tested.
The one kind prepared in table 1,1~example of embodiment 9 can be used for alkaline polymer electrolyte fuel cell and all-vanadium flow
The correlated performance of the polyether sulfone anion-exchange membrane of battery：
Claims (4)
1. a kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell, it is characterised in that such as formula
(I) polyether compound containing cyclohexane group and quaternary ammonium salt side shown in：
Wherein m and n represents the degree of polymerization, m=1~200 and n=0~200, and 0<M/ (m+n)≤1, the relative molecular weight of polymer are
10000~100000；
DescribedThe one kind being each independently selected from formula (2)~formula (3)：
R1=R2=H；
Any one in formula (4)~formula (6)：
Q=methyl or quaternary ammonium salt group.
2. a kind of polyether sulfone anion-exchange membrane available for alkaline polymer electrolyte fuel cell, it is characterised in that be such as formula
(I) polyether compound containing cyclohexane group and quaternary ammonium salt side shown in：
Wherein m and n represents the degree of polymerization, m=1~200 and n=0~200, and 0<M/ (m+n)≤1, the relative molecular weight of polymer are
10000~100000；
DescribedThe one kind being each independently selected from formula (2)~formula (3)：
R1=Q, R2=H or R1=H, R2=Q or R1=R2=Q, wherein Q=methyl or quaternary ammonium salt group；
Any one in formula (7)~formula (9)：
A kind of 3. polyether sulfone anion exchange available for alkaline polymer electrolyte fuel cell as claimed in claim 2
Film, it is characterised in that when Q is quaternary ammonium salt group, be specifically following several substituents in any one：
Wherein X is the anion with negative one valence charge, is Br-, Cl-Or OH-。
A kind of 4. polyether sulfone anion available for alkaline polymer electrolyte fuel cell as described in claim 1 or 2 or 3
Exchange membrane is applied in alkaline polymer electrolyte fuel cell and all-vanadium flow battery.
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| CN106633032B (en) * | 2016-09-23 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | A kind of cross-linking type alkalinity polyarylether anion-exchange membrane and the preparation method and application thereof |
| CN109320692B (en) * | 2018-09-21 | 2020-01-31 | 中国科学院长春应用化学研究所 | polyfluorene alkylene containing cation group and no ether bond, preparation method thereof and anion exchange membrane |
| CN112349940A (en) * | 2020-09-21 | 2021-02-09 | 长春工业大学 | Quaternary ammonium and imidazole cross-linked anion exchange membrane for fuel cell and preparation method thereof |
| CN114874420B (en) * | 2022-06-29 | 2024-02-13 | 中国科学院长春应用化学研究所 | Polymer and preparation method thereof, anion exchange membrane and fuel cell |
| CN115449108B (en) * | 2022-10-14 | 2023-11-17 | 中国科学院福建物质结构研究所 | proton exchange membrane |
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